Merging organometallic chemistry with polyoxometalate chemistry

A series of polyoxomolybdate-incorporated organometallic complexes has been obtained by reaction of [MBr(CO)5] or solvated M(CO)3+ ions (M = Mn or Br) with (nBu4N)2[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)3 (R = Me or CH2OH). Their molecular structures are related to those of previously described polyoxoalkoxomolybdates through the formal replacement of fac-MoO2(OR)+ units by topologically equivalent fac-M(CO)3+ units. Representative pairs of structurally related clusters include [Mo2O6(OMe)4-Re(CO)32]2- and [Mo4O10(OMe)6]2-, [Mo2O4MeC(CH2O)32Mn(CO)3]- and [Mo3O6(OMe)MeC(CH2O)32]-, [Mo2O4HOCH2C(CH2O)32Mn(CO)32] and [Mo4O8(OEt)2MeC(CH2O)32], [Mo6O16(OMe)2MeC(CH2O)32-Mn(CO)32]2- and [Mo8O20(OMe)4-MeC(CH2O)32]2-. Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb-like structure, the alternative cubane-type arrangement is observed in [Mo2O5(OMe)5M(CO)32]-.